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Duplex Stainless Steel: A Critical Review of

Metallurgy, Engineering Codes and Welding Practices

Ramesh Bapat, CMfgE, P.E.


Chief Engineer I, Western Region Materials Engineering
FMC Technologies
ramesh.bapat@fmcti.com

Pradip Goswami, P.Eng., IWE


Welding and Metallurgical Specialist
Ontario, Canada
pgoswami@sympatico.ca

October 17,2012

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Agenda

1. Safety / Quality Moments


2. Introduction
3. Metallurgy
4. Corrosion Resistance / Testing Methods PREN, PREW
5. CCT / CPT Temperatures
6. Design Codes and Specifications
7. Role of Alloying Elements
8. Welding of Duplex and Super Duplex
9. Micrograph and Schaffer Diagram
10. Concluding Remarks
11. References
12. Acknowledgements

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Introduction

There are four (4) types of duplex lean duplex (20%Cr), duplex (22%Cr), super
duplex (25%Cr) and hyper duplex (30%+Cr)
Lean duplex is better than 316 grade stainless steel but not as good as duplex
Duplex has widespread application in offshore oil and gas, petrochemical and
other industries due to high strength, excellent resistance to SCC and good
weldability
Presence of dual microstructure ferritic / austenitic; excellent corrosion
resistance and strength, pitting resistance and resistance to chloride stress
cracking
Applications down hole tubulars, flow lines, manifolds
Maximum operating temperatures; limited to 230C (447F)

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Metallurgy of Duplex Stainless Steels (DSS)

DSS solidify as fully ferritic, some of which transforms to austenite as temperature


falls to 1000C (1832F)
Nitrogen promotes austenite formation from the ferrite at a higher temperature;
however, while cooling, carbides, nitrides, sigma and other intermetallic phases
are possible (microstructural constituents)
Solidification diagram of DSS Fe-Cr-Ni system at 68% iron

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Corrosion Resistance

DSS exhibit a high level of corrosion resistance in most environments


If microstructure contains at least 35% ferrite, duplex grades are more resistant to
chloride stress cracking than austenitic grades like 304 and 316. Ferrite is
susceptible to hydrogen embrittlement; hence, duplex grades are not suitable
where hydrogen may be charged into the metal
In the 1980s, a higher alloyed DSS grade was developed called super duplex
Super duplex grades are made to withstand more aggressive environments, but
bear risk of precipitating unfavorable phases due to higher alloying elements
Super duplex grades are usually characterized by a Pitting Resistance Equivalent
Number (PREN) higher than 40
The higher the PREN number, the better the corrosion resistance
PREN= (%Cr) + (3.3x%Mo) + (16x%N)
PREW= (%Cr) + (3.3x%Mo) +(0.5%W) + (16x%N)

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Role of Alloying Elements in Duplex

Chromium (Cr) Ferrite Stabilizer A minimum of 10.5% chromium is necessary to


form a stable passive film to protect steel from mild atmospheric corrosion. The
corrosion resistance is higher with increasing chromium content
Molybdenum (Mo) Ferrite Stabilizer Molybdenum acts to support chromium to
provide chloride corrosion resistance and resistance to pitting corrosion;
molybdenum also resists tendency to form detrimental intermetallic phases (e.g.:
sigma, chi)
Nickel (Ni) Changes lattice structure from BCC to FCC; FCC gives excellent
toughness; Ni additions help delay the formation of detrimental intermetallic phases
Nitrogen (N2) Austenite Stabilizer It delays formation of sigma phase; increases
resistance to pitting and crevice corrosion; increases toughness; nitrogen is adjusted
based on nickel content to achieve desired phase balance
Manganese (Mn) Somewhat controversial; stabilizes austenite, but may reduce
pitting corrosion resistance

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Resistance to Acids

DSS have good corrosion resistance against strong acids


Both 2205 and 2507 DSS outperform many high nickel austenitic stainless steels in
solutions containing up to approximately 15% acid
DSS do not have sufficient nickel to resist the strong reducing conditions of mid-
concentration of hydrochloric acid
Their resistance to oxidizing conditions makes DSS viable candidates for nitric acid
service and strong organic acids
The DSS are also used in processes involving halogenated hydrocarbons because of
their resistance to pitting and stress corrosion

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Resistance to Caustics

The high chromium content and presence of ferrite provides for good performance of
duplex stainless steels in caustic environments
At moderate temperatures, corrosion rates are lower than those of the standard
austenitic grades

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Pitting and Crevice Corrosion Resistance

DSS can be characterized by a temperature above which pitting corrosion will initiate
and propagate within approximately 24 hours to a visibly detectable extent
This temperature is known as Critical Pitting Temperature (CPT)
Pitting initiation below this temperature will not occur for long periods of time
Pit initiation is random, and the CPT is sensitive to minor variations
With a new research tool described in ASTM G 150, CPT can now be accurately and
reliably measured by electro potential measurements

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Pitting and Crevice Corrosion Resistance (Contd.)

The critical temperature for initiation of crevice corrosion is called the Critical Crevice
Temperature (CCT)
Dependent on the individual sample of stainless steel, chloride environment and
nature of the crevice
Geometrical factor of the crevices causes more scatter for the measurement of
CCT than for the CPT
CCT could be 15 to 20C (27 to 36F) lower than the CPT
Generally, higher critical pitting or crevice corrosion temperatures indicate greater
resistance to the initiation of these forms of corrosion
CPT and CCT in welded condition would be expected to be somewhat lower than the
equivalent base metal. It is advisable for the welding consumable to be slightly
overmatching compared to the base metal.( e.g. 2205 grade base metal is welded
with 2209 welding consumable)

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Pitting and Crevice Corrosion Resistance (Contd.)
CPT and CCT of 2205 and all other grades of DSS are well above those of Type 316
This makes 2205 and other DSS / SDSS a versatile preferred material for
applications involving chlorides and H2S environment (Refer MR0175/ISO 15156-
3, Table A24)
For critical seawater applications involving superior corrosion resistance, the
SDSS are extremely popular compared to higher alloyed austenitic grade stainless
steels
CPT = Constant + %Cr + 3.3x%Mo + 16x%N (Per IMOA guidelines)

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Resistance to Stress Corrosion Cracking

In many refining, petrochemical process industries, DSS are replacements for


austenitic grades in applications with a significantly lower risk of SCC
DSS/SDSS are generally not susceptible to stress corrosion cracking in oil and gas
production environment
Examples of environments in which SCC of DSS may be expected, including the boiling
42% magnesium chloride test, are shown below

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Requirements of Design Codes and Specifications

DSS can have good notch toughness for low (arctic) temperature and ambient
temperatures, but not for cryogenic applications
Minimum allowable temperatures are 51C (60F) in the B31.3 Code
Minimum allowable temperatures are 29C (20F) for some cases in the ASME
Section VIII Code
Actual limits are determined by reviewing the applicable code

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Requirements of Design Codes and Specifications
(Contd.)

ASME Section VIII requirements for impact testing for DSS base and weld metals are
given in UHA-51(d) (3)
Requires impact testing of all DSS thicker than 10 mm (3/8 in.) or those with a
Minimum Design Metal Temperature (MDMT) less than 29C (20F)
Maximum operating temperatures are limited by the susceptibility of the sigma
phase embrittlement
Most design codes applicable to refinery and oil and gas processing plants limits
upper application temperature of various DSS grades to between 260C to 300C
(500F to 572F) as long as it is intermittent and not continuous

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Requirements of Design Codes and Specifications
(Contd.)

Code limit applies to the risks associated with continuous long-term exposures
above the limiting temperature
Brief infrequent excursions of the actual metal temperature into the
embrittlement range may be tolerated without significant loss of properties
Damage from overheating is cumulative; the code does not address the issue
Typical design limits for DSS and SDSS are specified below

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Welding of Duplex and Super Duplex SS

Duplex and super duplex stainless steels are weldable by all conventional arc welding
processes such as:
Shielded Metal Arc Welding (SMAW) is particularly excellent for position
welding, single-sided welding and weld joints where access is limited
Gas Metal Arc Welding (GMAW) is a particularly good method for welding sheet
metal up to around 6 mm thick
Gas Tungsten Arc Welding (GTAW) is normally used for thin (up to around 4 mm)
work pieces; it is specifically common in the welding of pipe joints
Flux Core Arc Welding (FCAW) is suitable for material thicknesses above
approximately 2.5 mm
Submerged Arc Welding (SAW) is widely used with duplex steels due to its high
productivity, and the beautiful weld finishes are advantageous

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Welding of Duplex and Super Duplex SS (Contd.)

Welding duplex and super duplex stainless steels to design code / specification
requirements is challenging to any welding engineer
Common arc welding processes are suitable for joining duplex and super duplex
stainless steels depending on process and economy related conditions as narrated
below

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Welding of Duplex and Super Duplex SS (Contd.)

Recommended shielding gases for MIG, TIG, FCAW for duplex / super duplex stainless
steels

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Commonalities for DSS / SDSS
Duplex stainless steel has an approximate
balanced 50/50 microstructure obtained by
controlled chemical composition and heat
treatment
Austenite / ferrite spacing is important to
prevent Hydrogen Induced Stress Cracking
(HISC)
30 microns austenite/ferrite spacing is usually
considered good for forgings; 10 microns for
small diameter tubing
Micrographs of both duplex and austenitic
alloys are shown to the right (common
industry practice ferrite is normally 40 60%)
The Schaeffer Diagram shows the predicted
ferrite content of various duplex weld metals
Ni Equivalent=%Ni+30x%C+0.5% Mn

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Concluding Remarks

Duplex stainless steels are extremely versatile and are engineering alloys of very
high integrity
Careful selection of these alloys for the right design and service environment
leads to much better performance, design life and higher integrity
The modern duplex stainless steels have as good weldability as the austenitic
stainless steels
Good corrosion resistance and mechanical properties of DSS are the result of well
crafted WPS / PQR that define heat inputs and cooling rates to achieve weldments
with optimum ferrite to austenite balance
The presence of ferrite in DSS imparts the superior chloride SCC resistance and
high strength
Austenite in DSS provides higher resistance to aqueous corrosion and low
temperature impact toughness

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Concluding Remarks (Contd.)

The recommended phase balance of DSS and SDSS should contain 40% 60%
ferrite in the base metal and the weld metal
For DSS, too low and too high heat inputs should both be avoided, as both
extremes can lower the corrosion resistance
Nitrogen additions to the shielding gas and the purging gas can be used with
advantage, when a higher corrosion resistance is desired in the weld, than
normally can be obtained by pure argon

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References

1. API Technical Report 938-C. 2005. Use of Duplex Stainless Steels in the Oil Refining
Industry.
2. The History of Duplex Developments. J. Charles and P.Chemelle. 8th Duplex
Stainless Steels Conference. 13-15 October 2010. Beaune, France.
3. The Physical Metallurgy of Duplex Stainless Steels. J.O. Nilsson and G. Chai.
Sandvik Materials Technology.
4. Practical Guidelines for the Fabrication of Duplex Stainless Steels. International
Molybdenum Association.
5. Welding Duplex and Super Duplex Stainless Steels. L. van Nassau, H. Meelker and
J. Hilkes.

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Acknowledgements

Thanks to FMC Management and particular thanks to the following experts for
their support of this paper: Brian SKEELS, Greg Glidden, Michael Coles, Elliott
Turbeville, Joel Russo, Tina Kruse, Mike Robinson, Mike Williams, Randy Shipley,
Randy Wester and Jill Bell.
Thanks to the organizing committee of the Stainless Steel World Americas 2012
conference for the opportunity to present this paper.

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